| Summary: | Abstract In this study, a facile strategy to promote electrochemical performance of free‐standing Li‐ion battery electrode composed of titanium dioxide (TiO2) via composite formation with reduced graphene oxide (RGO) using ultrafast and self‐expansion reduction reaction (USER) was proposed. This approach induced self‐expansion through rapid heating providing abundance of cavities/empty spaces to alleviate volume change during charge/discharge process resulting in boosted storage and conversion response of the system (765 mAh g−1 at 0.05 A g−1) and accelerated Coulombic efficiency. Detailed electrochemical, microscopic and structural analyses (ex‐situ) of the film prove that this internal expansion delivers enhanced ionic diffusion and shielding material from volume changes during charge/discharge process. Therefore, we believe that this simple and very fast strategy offers a venue to overcome one of the main bottleneck in promotion of electrochemical performance of other active materials which are sensitive to volume expansion during lithiation/delithiation process.
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